US3640937A - Linear segmented polyurethane elastomers - Google Patents

Linear segmented polyurethane elastomers Download PDF

Info

Publication number
US3640937A
US3640937A US830128A US3640937DA US3640937A US 3640937 A US3640937 A US 3640937A US 830128 A US830128 A US 830128A US 3640937D A US3640937D A US 3640937DA US 3640937 A US3640937 A US 3640937A
Authority
US
United States
Prior art keywords
parts
nco
solution
filaments
elastomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US830128A
Other languages
English (en)
Inventor
Wilhelm Thoma
Bergisch Neukirchen
Harald Oertel
Heinrich Rinke
Ulrich Bahr
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Application granted granted Critical
Publication of US3640937A publication Critical patent/US3640937A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6521—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step

Definitions

  • This invention relates to highly elastic linear segmented polyurethanes comprising segments obtained from certain semi-carbazide hydrazides chain extending agents, highly elastic fibres thereof and to a process for the preparation of said linear, segmented polyurethane elastomers.
  • substantially linear, relatively high molecular weight NCO-terminated preadducts (hereinafter referred to in short as NCO-pr'eadducts or NCO- prepolymers), prepared from relatively high molecular weight polyhydroxy compounds (optionally in the presence of relatively small quantities of low molecular weight diols) and excess molar quantities of organic diisocyanates, can be reacted in highly polar organic solvents such as dimethyl formamide with substantially bifunctional chain extenders containing two active hydrogen atoms, resulting in the formation of viscous solutions of substantially linear polyurethane elastomers which can be processed from the solution and converted into elastic filaments or films.
  • NCO-pr'eadducts or NCO- prepolymers prepared from relatively high molecular weight polyhydroxy compounds (optionally in the presence of relatively small quantities of low molecular weight diols) and excess molar quantities of organic diisocyanates
  • Suitable chain extenders include in particular diamines, preferably aliphatic or araliphatic diamines, hydrazine or dihydrazide compounds.
  • Diamines and hydrazine are highly reactive with respect to the NCO- preadducts which preferably comprise aromatically linked NCO groups, with the result that non-uniform crosslinked components (jellyfish) are likely to be formed in the elastomer solution.
  • NCO- preadducts which preferably comprise aromatically linked NCO groups
  • elastomer filaments of this kind are sensitive to the presence of traces of heavy metal ions. This occurs for example when carbodihydrazide is used as chain extender in the reaction with NCO-preadducts. Boiling with water containing copper ions in small quantities, for example, is sufficient to produce a change in the colour of the filaments to pinkish-red, spoiling the appearance of undyed fabrics, even if there is no evidence of the strength property being affected.
  • Oxalic acid dihydrazide is almost insoluble in dimethyl formamide and, after re action with NCO-preadducts, gives elastomer filaments which, like filaments containing units from malonic acid or succinic acid dihydrazide chain extenders, are extremely sensitive to hydrolysis and are not sufficiently resistant to strain under hydrothermal conditions.
  • ethylene bis-semicarbazide or hexamethylene bis semicarbazide for example is used instead of the dihydrazide compounds as chain extender in the reaction with the NCO-preadducts, the elastomer solutions obtained cannot be spun because they become gel-like in consistency after a short time, or even during their preparation.
  • the polyurethane elastomers formed are probably inadequately solvated by the solvent with the result that they are precipitated in the form of a pasty gel which is either impossible or extremely diificult to convert into filaments or films.
  • a further object of the invention is an essentially linear segmented polyurethane elastomer consisting of a reaction product of an essentially linear relatively high molecular weight NCO-preadduct and a chain extending agent selected from the group consisting of and a conventional chain extending agent selected from the group consisting of water, hydrazine, a glycol, an amino alcohol, a diamine, and a dihydrazide.
  • Polyurethane elastomers extended with B-semicarbazide propionic acid hydrazide have particularly outstanding properties, with the results that this hydrazide is preferably used as the bifnnctional compound containing two active hydrogen atoms for chain extending the NCO-preadducts, particularly in cases where the polyurethanes are to be converted in elastomeric filaments.
  • elastomers such as these give high-grade elastomeric filaments with substantially improved thermal and hydrothermal properties, coupled with outstanding strength and elastic properties.
  • the filaments and films are colour stable in the presence of heavy metals, for example copper ions, and are much more resistant to hydrolysis than comparable dihydrazide compounds.
  • the polyurethane elastomers are readily soluble in the usual solvents, such as dimethyl formamide or dimethyl acetamide.
  • the compound preferably used as chain extender namely B-semicarbazide propionic acid hydrazide
  • chain extender namely B-semicarbazide propionic acid hydrazide
  • Even minor changes in structure, for example with progression in the homologous series to "ysemicarbazide butyric acid hydrazide (x 3 in the above formula), are sufiicient to reduce the properties of the elastomers chain-extended in this way in connection with their behaviour under thermal and hydrothermal CQIldiv tions, to below the adequate limit, for example, for elastomeric filaments.
  • the outstanding properties of the products' is only obtained with aliphatic semicarbazide hydrazide.
  • a further object of the invention are the following processesfor ,preparingpolyurethane elastomers containh ri v w -NHCQ'NH+(C Q)X,- I
  • the products obtained by the process are linear, seg
  • mented polyurethane elastomers consisting of intralinear, segments of the structure I in which D represents a long chain, divalent substantially aliphatic polymer radical without any substituents reactive to isocyanate, and having a molecular .weight of from 600 to 5000 and a melting point below '60" C.; R reprsents a divalent organic radical of an aromatic, aliphatic, cycloaliphatic or araliphatic diisocyanate;G repre-' sents a divalent aliphatic cycloaliphatic or aralip'hatic radical of a dialcohol with molecular weight of from 62 to 300, preferably containing one or more tertiary aliphatic amino groups, without the :terminal hydroxyl groups; r is an integer of at least 1, e.g. from 1 to 5,
  • linear segmented polyurethane elastomers may preferably polycarbonates or poly:-N-alkylurethanes,- other groups consist of intralinear segments'tof structure II which are suchas ester,- ether, amide, urethane, N-alkylurethane obtained by reacting the NCO-preadducts with convengroups optionally being present in'the above-compounds, tional chain extenders such as water or compounds conwith molecular weights of from 600 to'5000. and aining two terminal NH groups and.
  • polyesters of adipic acid and H dialcohols are particularly useful, if desired, mixtures of dialcohols, for ex- H2N Z N 2 ample ethylene glycol, propylene glycol, 1,4-butane diol,
  • Polyesters of narrow molecular weight distribution (obtained by polymerising capro- 2)s 2 8 lactones with glycols) are also eminently suitable start- L, H ing materials.
  • Polyurethane elastomers that are highly resistant to hydrolysis can be obtained from polyalkylene ethers such as polytrimethylene ether diols, polypropylene glycols,
  • Polyepichlorhydrins with terminal OH-groups in cis/ trans mixture the aforementioned molecular weight range are also suit- CH /OH mdial able for use in production of fireproof end products.
  • Basic CHFCHg polyethers whose tetriary amino groups may be a divalent aromatioradical without any condensed i quaternised at least in part, are also suitable.
  • Aromatic diisocyanates of symmetrical structure are particularly suitable examples, including a divalent aralrphatrc radical, preferably a 1,3 or 1,4 p y methane diisocyanate; p y dimethyl methane 4,4 diisocyanate, phenylene-1,4-diisocyanate;
  • yzo 1, a radical HN CO CO .NH diphenyl l,4 diisocyanate; diphenyl ether-4,4-diisocya- 1 1 C NH i hi nate or their alkyl-, alkoxylor halogen-substituted derivais a divalent organic radical with up to 13 carbon atoms, fives; 9 y Y -d y for example an aliphatic, cycloaliphatic or aromatic thflr commefclal f s P PY p ffyl n radical, preferably a 1,3-d11socyanate, m-xylene dnsocyanate, p-xyleue d isocyamate and a,a,a',a'-tetramethyl-p-xylene diisocyanate.
  • mire T I addition one may also use the alkyl or halogen-substituted CH CH3 products of the above-mentioned diisocyanates, for example 2,5-dichloro-p-xylene diisocyanate or tetrachloro-pphenylene diisocyanate, dimenc tolylene-2,4-d11socyanate OH,-N N-orr,- 0H, ,-o0-NH or bis-3-methyl-4-isocyanatophenyl urea.
  • diisocyanates for example 2,5-dichloro-p-xylene diisocyanate or tetrachloro-pphenylene diisocyanate, dimenc tolylene-2,4-d11socyanate OH,-N N-orr,- 0H, ,-o0-NH or bis-3-methyl-4-isocyanatophenyl urea.
  • Aliphatic 'diisocyanates such as hexane-1,6-diisocyanate, cyclohexane-1,4- radical diisocyanate, dicylohexylmethane-4,4'-diisocyanate, l-iso
  • suitable relatively high molecular weight cyanato 3 is0cyanatomethyl-3,5,5-trimethyl cyclohexane substantially linear polyhydroxyl compounds with teror 2,2,4-trimethyl hexane-1,6-diisocyanate may also form minal hydroxyl groups (or formula HO-DOH) inat least part of the isocyanates used and, following exponate and dicyclohexylmethane:4,4-diisocyanate, are preferably used.
  • diisocyanates are reacted with the diisocyanates in excess molar quantities, for example in a molar ratio of 1: 1.25 to 1:4.0, preferably from 1:1.30 to 1:25, with the diisocyanates optionally added in stages, in the melt or in the solvents inert with respect to isocyanates such as tetrahydrofuran, dioxan, ethyl acetate, butanone-2 or chlorobenzene, dimethyl formamide, at temperatures of from about to 130 C. and preferably at temperatures of from to 100 C.
  • isocyanates such as tetrahydrofuran, dioxan, ethyl acetate, butanone-2 or chlorobenzene, dimethyl formamide
  • the diisocyanates are preferably reacted in lower molar ratios, for example from 1:1.25 to 112.0. They are preferably used in higher molar ratios, for example from 1:15 to 2.5 in cases where they have relatively high molecular weights.
  • the same structure is obtained in cases where the polyhydroxyl compounds are initially reacted with an OH/NC'O ratio of 2:1 and the new pre-extended dihydroxy compound subsequently converted into the NCO-preadduct, optionally in conjunction with another diisocyanate, with an OH/NCO ratio of 1:2. With other molar ratios, statistical mixtures of corresponding NCO- preadducts can be formed.
  • relatively small quantities of low molecular weight diols with molecular weights of from 62 to about 300, in particular those which contain one or more tertiary amino groups, may be used together with the relatively high molecular weight polyhydroxyl compounds HODOH for the reaction with the diisocyanates.
  • the diols may be added either in admixture with the relatively high molecular weight polyhydroxyl compounds or at any time during or even after the NCO-preadduct has been formed from thediisocyanate and relatively high molecular weight polyhydroxyl compounds.
  • Suitable diols include, for'example, ethylene glycol, 1,4-butane diol, bis- N,N 3- hydroxyethyl)-methyl amine; bis-N,N-(,6-hydroxypropyl) -methyl amine; N,N-dimethyl-N,N-bis(B- hydroxy ethyl)-ethylene diamine; N,N'-dimethyl-N,N'- 'bis-(fi-hydroxy propyl)-ethylene diamine; N,N'-bis-(/8-hydroxy propyl)-piperazine; N,N'-bis-( 8-hydroxy ethyl)- piperazine or hydroquinone-bis-(fl-hydroxy ethyl ether).
  • diols containing tertiaryzamino groups improves in particular the aflinity for dyes and'fastness to light of the products and provides a starting point for other after treatments, for example the crosslinking reaction with 4,4'-dichloro methyl diphenyl ether.
  • the low molecular weight diols are generally used i quantities of from 0.01 to 1.0 mol and preferably in quantities of from 0.05 to 0.5 mol. They may be used to particular advantage in quantities of from 0.07 to 0.25 mol per mole pf polyhydroxyl compound in the formation of the NCO-preadduct. Inthese cases, the quantity in which the diisocyanate used is preferably increased to beyond the molar ratios which have just been specified by an amount corresponding to'the low'molecular weight diols, for example, by 0.01 to 1.0 mol.
  • NCO-preadducts with the structure or in the case of pre-extension in the formation of an NCO-preadduct with the structure
  • typical structural segments of the NCO-preadducts (which may also be termed relatively high molecular weight diisocyanates) which arise out of pre-extension or glycol incorporation, are formed in a more or less statistical sequence and may optionally occur in multiple repetition.
  • the number of NCO groups present in the NCO-preadducts is of decisive importance to the properties of the polyurethane elastomers obtained from them. Generally speaking, it is only those NCO- preadducts whose NCO content in the solid amounts to at least 1.0%, that are suitable for reactions with the semi-carbazide hydrazides to be used as chain extenders in accordance with the invention.
  • the NCO-preadducts should preferably contain from 1.5 to about 6% by weight of NCO. NCO contents of from 1.75 to 3.5%, based on the solids content of the NCO-preadduct, are particularly preferred in cases where the elastomers ob tained from them are to be used for the production of elastomer filaments.
  • ,B-Semicarbzizide pro NH -groups of the formula H N-Z--NH in which Z ganic compounds with two' terminal NH groups, such.
  • Suitable conventional chain extenders include water, glycols, amino alcohols or preferably oras hydrazine (or hydrazine hydrate), aliphatic diamines, preferably ethylene diamine, l,2-propylene diamine, cisand/or trans-1,3-diaminocyclohexane, N,N-bis-(y-aminopropyl)-methyl amine; N,N' dimethyl N,N' bis-(yaminopropyl) ethylene diamine; N,N' dimethyl-N,N-' blS (y aminopropyl)-piperazine; N,N' bis (y-aminopropyl) 2,5 dimethyl piperazine, aromatic diamines, preferably 4,4 diamino diphenylmethane; 4,4 diamino diphenyl ether, 4,4'-diamino diphenyl ethane, or' 4,4fd iamino diphenyl dimethylmethan
  • the NCO-preadducts are reacted with the chain extenders in substantially stoichiometric equivalent quantities (based on the NCO content), for example in quantities of from 100 to 120% and preferably in quantities of from 100-to 110 mol percent of chain extenders, advantageously at temperatures of from about to 130 C. and preferably at temperatures of from 20 to 80 C., in the presence of solvents.
  • the required molecular weight and solution viscosity may be adjusted by the careful addition of other preferably less reactive aliphatic dior tri-isocyanates (according to German patent specification No. 1,157,386).
  • the still unreacted terminal groups may he stabilised by reaction with mono isocyanates such as butyl isocyanate, carboxylic acid anhydrides or other acylating substances such as acid chlorides or carbamic acid chlorides, e.g. acetanhydride, phthalic acid anhydride, acetylchloride.
  • mono isocyanates such as butyl isocyanate, carboxylic acid anhydrides or other acylating substances such as acid chlorides or carbamic acid chlorides, e.g. acetanhydride, phthalic acid anhydride, acetylchloride.
  • Suitable solvents in which the process of the invention may be carried out include highly polar, organic watersoluble solvents which contain amide, urea or sulphonic groups, are capable of forming, strong hydrogen bridge bonds and which preferably have boiling points of from about 140 to 225 C., for example dimethyl formamide, diethyl formamide, dimethyl acetamide, N-formyl morpholine, hexamethylphosphoramide, tetramethyl urea, dimethyl sulphoxide, dimethyl cyanamide or mixtures thereof.
  • dimethyl formamide or dimethyl acetamide is preferably used as the solvent.
  • polar solvents which on their own are not able to dissolve the polyurethanes and polyurethane ureas, for example tetrahydrofuran, dioxan, acetone, ethylene glycol, monoethyl ethe'r acetate or chlorobenzene, may be added to the highly polar .solventsinquantities of up to 33% by weight of the total amount of solvent.
  • the semicarbazidehydrazides are advantageously first dissolved in a minor amount of water (such as twice the weight ofsemicarbazide-hydrazide) and then diluted with the highly polar organic solvents (such as dimethyl formamide).
  • the concentration of the elastomer solutions should amount to between about and 43% by weight, preferably to be tween and 33% and more, preferably to between and 28% by weight, with the viscosities lying between l and 3000 poises/ 'C. and preferably between about 50 and 800 poises/20" C.
  • the molecular weight of the segmented elastomers according to the invention should be so high that the inherent viscosity as measured at C. I 7 I "A I amounts touat least 0.5 and preferably to between 0.70 and ,1.'9 'when;determinedwith a solution of 1.0 g, of elastomer which has :beendissolved in 100 ml.
  • 1 is the relative viscosity-(ratio of the through-flow time of the solution to. the through-flow time of the solvent) while C is the concentration in g./100 ml.
  • the melting points of the elastomers, as determined on Kofler'benches, should b above 200 .C.. and preferably above 220 C. in cases where they are to bev used as starting materials for elastomer filaments.
  • the solutions of the polyurethanes and polyurethane ureas may have added to them organic or inorganic pigments, dyes, optical brighteners, UV-absorbers, phenolic antioxidants, special UV-absorbers such as N,N-dialkyl semicarbazides or N,N-dialkyl hydrazides and crosslinking substances, for example paraformaldehyde, melamine hexamethylol ether or other formaldehyde derivatives such as dimethylol dihydroxy ethylene urea, dimethylol ethylene urea, trimethylol melamine and dimethylol urea dimethyl ether, quaternising agents, for example dichloromethyl durol or polyaziridine ureas, for example hexamethylene-w,w-bis-ethylene imide urea.
  • the resistance to the dissolution and the swelling effect of highly polar solvents is modified for example by using a thermally initiated crosslinking reaction.
  • the solvent may be removed from the elastomer solutions by a variety of methods known per se, including evaporation or coagulation, in some cases accompanied by formation of the required shaped product such as filaments or foils.
  • Films or coatings are produced by allowing the elastomer solution or dry on substrates, for example glass plates or textile products. Filaments can be obtained by wet or dry spinning.
  • Microporous coatings are obtained by coating elastomer solutions or water-containing dispersions on to (optionally textile) substrates, eventually holding the coated polyurethane in an atmosphere of moist air for some time followed by coagulation in non-solvents for the polyurethane, for example water, organic solvents or mixtures thereof.
  • the microporosity of the films can be increased by use of suitable additives such as finely divided salts, emulsifiers or soluble polyamides.
  • Films By brushing the elastomer solution on to glass panels and allowing it to dry (30 minutes at C., +45 mins. at 100 C.), final thickness from about 0.15 to 0.25 mm. Some filaments of from about 250 to 800 den. thick were cut out of the films by means of a film-cutting machine and measured.
  • Wet spinning process An elastomer solution, preferably of 20% by weight concentration is spun at a rate of about 1 ml./min. through a 20-hour spinnerette (bores 0.12 mm. in diameter) into a coagulating bath heated to -85 C. of by Weight of water/ 10% by weight of dimethyl formamide (length approximately 3 m.), and wound up at a take off rate of 5 m. per minute after passing through a washing zone (water/90 C.). The bundles are stored in boiling water (50 C. for 1 hour) and then dried.
  • Dry spinning process A preferably 24 to 26% by weight elastomer solution is spun through a 16-hole spinnerette (bore-diameter 0.20 mm.) into a shaft 5 m. long heated t0"220-250 C. into which air heated to between 210 and 280 C. is blown.
  • the filaments are run off at a rate of about m..per minute and, following treatment with a talcum suspension, optionally accompanied by stretching, are wound up for example at a rate of to m. per minute.
  • the filaments may then be heat treated either while on bobbins or in continuous form.
  • 1 1 Elongation at break is measured in a tensile testing machine. The distance between the grips is monitored by a light barrier, and the amount of slip duly compensated.
  • the modulus at 300% is shown in the first elongation curve, the modulus at 150% in the third recovery curve, whilst the permanent elongation is determined after three times 300% elongation, 30 seconds after relaxation.
  • the heat distortion temperature (HDT) of elastomers is determined as follows: The denier of elastomeric filaments laid out for some 3 hours under normal climatic conditions completely free of tension, is determined by weighing a 450 mm. long length of filament under an initial strain of 0.05 m-g./ den.
  • An elastomeric yard is suspended at room temperature in a tube which contains air or is filled with nitrogen, under an initial load of 2 mg./den., the distance between the grips being 250 mm.
  • the tube is surrounded by a heating jacket through which flow a silicone oil heated and with its temperature thermostatically controlled.
  • the temperature inside the tube is first of all increased to about 125 C. over a period of about 30 minutes. Thereafter, the temperature is increased at a rate of 3 C. every 5 minutes until the elastomeric filament has undergone a change in length of more than 400 mm.
  • the measurements obtained are plotted in a graph in such a way that on the abscissa 1 unit of length corresponds to a temperature difference of C.
  • the heat distortion temperature is the temperature read off by vertically projecting the point of contact of the 45 tangent to the temperature/ length change curve on the abscissa.
  • the resistance of the elastomers to heat may be more highly assessed, the higher the I-IDT-value which is found.
  • the value should amount to at least 145 C. and preferably to higher than 150 C. 0
  • HWDT hot-water-induced decrease in tension
  • a length of filament held between grips 100 mm. apart is stretched by 100% at a temperature of 20 C. and the tension (mg/den.) produced in it after 2 minutes is measured (first value).
  • the filament still stretched by 100% is then immersed inwater heated to 95 C. and the tension produced after a residence time of 3 minutes is measured (second value). After this measurement, the filament is removed from the water bath and left for 2 minutes at room temperature. The filament still held between the grips is then released until free of tension and the permanent residual elongation measured (third value).
  • a weight of 30 mg./den. is attached by means of a clip through a 50 mm. long filament, and is left suspended in air for 25 minutes at room temperature. After 25 minutes, the percentage elongation is determined (first value).
  • the filament thus elongated is then immediately immersed in water heated to C. together with the weight attached to it and the elongation occurring under water is read off after an interval of 25 minutes. It is expressed as percentage elongation based on the distance between grips 50 mm. (second value).
  • the weighted filament is then removed from the hot water bath, after which its permanent residual elongation is determined by lifting the weight until the filament is free of tension (3rd value).
  • the semicarbazide acetic hydrazide is obtained in a crude yield of 91% of the theoretical. After recrystallisation from alcohol (2 ml./ g.) and water (1.5 ml./g.), pure colourless crystals are ob taine'd'in a yield of 71%, M.P. 167 C.
  • 1180 parts of phenyl chlorocarbonic acid ester are dissolved'in 3800 parts by volumeofmethylene chloride, and 700 parts of water are added torthe resulting solution whichis then cooled to 07 C.
  • 1228 parts of fl-alanine ethyl ester hydrochloride are added dropwise into the twophase system from a heated dropping funnel, a solution of 450 parts of potassium hydroxide and 1090 parts of potassium carbonate'in 2600 parts of Water being simultaneously run in. The dropwise addition takes about 60 minutes to complete.
  • the two-phase system is then stirred for 2 /2 hours without cooling, the phases are separated, the methylene chloride solution is dried over anhydrous sodium sulphate and finally the methylene chloride is distilled off.
  • the fl-carbethoxy ethylene carbamic acid phenyl 'ester is-an oil which crystallises after prolonged standing, M.P. 63 C., yield approximately 75% of the theoretical.
  • a solution of 1336 part of pcarbethoxy ethylene carbamic acid phenyl esterin 800 parts by volume of alcohol is introduced over a period of approximately 30 minutes into a boiling solution of 1900 parts of hydrazide hydrate and 480 parts by volume of alcohol. After boiling for 1% hours, the solution is cooled to 0 C., the crude ,B-semicarbazidopropionic acid hydrazide which has crystallized out is quickly filtered under suction and the filtrate is suspended in alcohol and is then sharply suction-filtered again. After drying, the crude yield amounts to 872 parts (965 of the theoretical).
  • Example I 1200 parts of a mixed polyester of adipic acid and a glycol mixture of 1,6-hexane diol/2,2-dimethyl propane diol in a molar ratio of 65:35 (OH number 68.0, M.P. 34-36 C.) are heated for 53 minutes to 9296 C. with 23.55 parts of N,N-bis-(,8-hydroxy propyl)methylamine, 335.4 parts of diphenyl methane-4,4-diisocyanate and 389 parts of chlorobenzene, and the resulting mixture is left to cool to room temperature.
  • the inherent viscosity of the elastomer subtance is 1.27, and its melting point (Kofler bench) 230 C.
  • the filaments turn dark-red-brown in colour following treatment with amomniacal CuSO solution.
  • the solution is pigmented with 4% TiO' (based on the solids content) and converted in the usual way into films or into filaments by dry or wet spinning.
  • the solid elastomer has an inherent viscosity of 1.12. Both the thermal and the hydrothermal properties are excellent.
  • the filaments do not undergo any decrease in strength under the normal conditions of hydrolysis (of. Example 1), and have a melting point of from 227-228 C.
  • Example 6 500 parts of the NCO-preadduct solution described in Example (1.73% NCO) are stirred over a period of 20 minutes into a solution heated to 65 C. of 15.50 parts of semi-carbazide acetic acid hydrazide in 891 parts of dimethyl formamide. After cooling, a uniform colourless elastomer solution with a viscosity of 189 poises is obtained. This is given a pigment content of 4% by the addition of TiO The viscosity rises to 561 poises after the addition of 15 parts of more NCO-preadduct solution. The elastomer has an inherent viscosity of 1.06.
  • Example 7 300 parts of a commercial caprolactone polyester with a molecular weight of 830 and a melting point of 38-40" C. (a product of the Union Carbide Company known as MAX 520) are heated for 50 minutes to 94-95 C. with 6.55 parts of N,N-bis-(B-hydroxy propyl)-methyl amine, 124.3 parts of diphenyl methane-4,4-diisocyanate and 185 parts of chlorobenzene.
  • MAX 520 a product of the Union Carbide Company
  • the resulting NCO-preadduct solution is then cooled to room temperature after which it contains 1.21% of NCO (corresponding to 1.725% of NCO in the solid substance 12.5 parts of fi-semicarbazide propionic acid hydrazide are dissolved in 882 parts of hot dimethylformamide. 500 parts of the above NCO-preadduct solution are stirred over a period of 10 minutes into this approximately 50 C. solution, resulting in the formation of a high viscosity homogenous elastomer solution. Following dilution with 51 parts of dimethylformamide and the addition of 4% of TiO (based on elastomer substance), the elastomer solution has a viscosity of 660 poises. The elastomer has an inherent viscosity 1;, of 1.26.
  • the data set out in Table 5 are obtained by casting the solution into films and spinning it in dry and wet spinning tests.
  • the filaments obtained show outstanding hydrothermal properties.
  • These elastomer filaments show a high resistance to hydrolysis. There is no decrease in tensile strength after hydrolysis for 16 hours in a washing solution of 2 g. per litre of soda and 5 g./I of soap heated to C.
  • Example 8 parts of a linear polycarbonate (OH number 122.5, molecular weight 915, melting point about 3035 C.), prepared by the high temperature condensation of diphenyl carbonate and a mixture of the diols 1,6-hexane diol and B-hydroxy ethoxyl-1-hexanol-6, in a molar ratio of 3:1, are first dehydrated and then heated with 9.5 parts of tolylene diisocyanate (commercial isomeric mixture 65:35) for 30 minutes to a temperature of 100 C. After the polyhydroxy compound has been dissolved in 100 parts of chlorobenzene, the resulting solution is heated for 30 minutes to 100 C. with 23.2 parts of 4,4'-diphenyl methane diisocyanate.
  • a linear polycarbonate (OH number 122.5, molecular weight 915, melting point about 3035 C.)
  • the NCO prepolymer solution has an NCO content of 1.40% (NCO content of solid: 2.46% 5.60 parts of ,G-serniearbazide propionic acid bydrazide are dissolved at 70 C. in 400 parts of dimethyl acetamide. 200 parts of NCO prepolymer solution poises/20 C.) are run into this solution with stirring.
  • the 18.9% viscous solution is pigmented with rutile (4% based on elastomer content) and is cast into films or wetspun to form elastic filaments.
  • the results of tests conducted on films and the results of tests on the wet-spun products are set out in Table 5. Graves tear propagation resistance as measured on films, amounts to 30 kg./cm., and microhardness to 65.
  • the elastomers have a melting point of 230 C.
  • Example 9 100 parts of the above-described polycarbonate are preextended -With 9.5 parts of tolylene diisocyanate, and then, following the addition of 100 parts of chlorobenzene, are reacted with 21.1 parts of 4,4'-diphenyl methane diisocyanate to form the NCO prepolymer.
  • Comparative test e.100 parts of the mixed polyester used in Example 1 (molecular Weight 1700') are first dehydrated and then admixed with 2.0 parts of N,-N' bis (p hydroxy propyl) methyl amine and 5 parts of chlorobenzene, and the resulting product is heated for 50 minutes to 100 C. with 29.2 parts of 4,4-diphenyl methane diisocyanate.
  • the NCO prepolymer is diluted with 95 parts of chlorobenzene, the solutionwhich has a solids content of 50%, has an NCO content of 1.38% (corresponding to 2.51% of NCO in the solid NCO-preadduct).
  • Example 11 l50 parts of the copolyester used in Example 1, which has an OH number of 68 and 37.2 parts of 4,4'-diisocyanato-diphenyl ether are heated for a period of 45 minutes to temperatures between 90 and 98 C. in a boiling water bath with 47 parts of chlorobenzene. After cooling to room temperature, the NCO-preadduct solution has an NCO content of 0.816%.
  • Example 12 14.7 parts of a-semicarbazide acetic acid hydrazide are dissolved at 100 C. in 1092 parts of dimethyl formamide and the resulting solution is mixed at 60 C. with 356 partsv of the 'NCO-preadduct melt of Example 4, the resulting mixture being homogenised by stirring. The solution is pigmented with 4% of "H (based on the solids content). 1.02 parts of 1,6-hexane diisocyanate and another 80 parts of dimethyl formamide are added to the viscous solution producing 'an increase in viscosity to 874 poises at 20 C.
  • the elasticity properties of the films are measured on cut filaments. As the results show (Table outstanding strength and elastic properties are obtained.
  • the elastomer substance does not show any signs of discolouration when boiled in tap water or after immersion for 5 minutes in 0.01 molar ammoniacal copper sulphate solution heated to 60 C.
  • the elastomer has a melting point of 213 C.
  • Example 13 800 parts of a mixed polyester of adipic acid and a mixture of ethylene glycol and 1,4-butane diol (molar ratio of the glycols 1:1), molecular weight 1980, melting point 33-37 C., are reacted for 100 minutes at 80 C. with 192 parts of diphenyl methane-4,4-diisocyanate and 174 parts of chlorobenzene to form 'a NCO-preadduct.
  • the solution has an NCO content of 2.56% (3.1%- of the NCO in the solid).
  • Example 14 22 Example 15 3.97 parts of B-semicarbazide propionic acid hydrazide are dissolved at 70 C. in 255 parts of dimethyl formamide and the resulting solution is mixed with 1.12 parts of m-xylylene diamine (molar ratio of the chain extenders 75 :25 103.5 parts of the NCO-preadduct solution described in Example 13 are introduced into this solution over a period of 4 minutes to form a homogenous highly viscous solution (450 poises/ C.). The elastomer solution is converted in the usual way into films or filaments (see Table 5 for results). The elastomer has a melting point of 237 C.
  • Example 16 107.5 parts of the NCO-preadduct solution used in Example 13 are introduced into a solution of 3.7 parts of fl-semicarbazide propionic acid hydrazide and 1.98 parts of 4,4'-diamino diphenyl ether (molar ratio of the chain extenders 70:30) in 259 parts of dimethyl formamide.
  • the resulting highly viscous elastomer solution is diluted with dimethyl formamide to a concentration of 20% (160 poises), and then converted into films and filaments (see Table 5 for results).
  • the elastomers have a melting point of 250 C., with softening from 241 C.
  • Example 17 1000 parts of the mixed polyester in Example 1 (hydroxyl number 67.4), 19.5 parts of N,N-bis-(/8-hydroxy propyl)-methylamine, 273.2 parts of diphenyl methane- 4,4'-diisocyanate and 327 parts of chlorobenzene are heated for 35 minutes to an internal temperature of 90- 99 C. After cooling, the NCOpreadduct solution has an NCO content of 1.93%.
  • Example 18 3.18 parts of B-semicarbazide propionic acid hydrazide are dissolved at 70 C. in 200 parts of dimethyl formamide and the resulting solution is admixed with 1.00 part of N,N'-bis-('y-amino propyl)-piperazine in 32 parts of dimethyl formamide (molar ratio of the chain extenders 80:20). 104.5 parts of the NCO-preadduct solution used in Example 17 are mixed in with intensive stirring, resulting in the formation of a homogenous colourless solution with a viscosity of 255 poises. The results of tests conducted on films and filaments are set out in Table 5. The product shows a high affinity for acid dyes with which it can be dyed fast.
  • Example 20 1000 parts of the polyester used in Example 1 (molecular weight 1655), 18.0 parts of N-N-bis-(fl-hydroxy propyl)-methylamine, 163.6 parts of p-phenylene dig 2mm mm u 2 N ww m5 2 2 8H 2% an d vw 3m ow mw m om 9 m3 2 cm 2: 3 mm Q 2 2. 3; we um Nd" m mw HS 2 mm m2 @mm vw o E 8 33 m2 2 mm c2 m5 and 3&3 u gm I!
  • a linear segmented polyurethane elastomer consisting of a reaction product of essentially linear, relatively high molecular weight NCO-prepolymers with chain extenders, comprising at least 55%, based on all the chain extending segments present, of a chain extending segment with the structure wherein x is 1 or 2.
  • a process for the production of substantially linear segmented polyurethane elastomers by reacting a NCO- preadduct containing from 1.0 to 6.0% by weight of NCO, prepared from relatively high molecular Weight dihydroxy compounds having a molecular weight from -600-5000 and a melting point below 60 C. and excess molar quantities of organic diisocyanates, with substantially equivalent quantities of bifunctional low molecular weight chain extending agents containing two hydrogen atoms in the presence of highly polar organic solvents, followed by removal of the solvents, the improvement comprises reacting aliphatic semicarbazide hydrazides of the formula wherein x is 1 or 2, as chain extenders.
  • a process for the production of substantially linear segmented polyurethane elastomers by reacting an NCO- preadduct, containing from 1.0 to 6.0% by weight of NCO groups, prepared from relatively high molecular Weight hydroxy compounds and low molecular weight diols with molecular Weights of from 62 to about 300, preferably containing tertiary amino groups in the molecule, in quantities of from about 0.01 to 1.0 mol per mol of relatively high molecular weight dihydroxy compound, and excess molar quantities of organic diisocyanates, with substantially equivalent quantities of bifunctional chain extenders containing two active hydrogen atoms in highly polar organic solvents, followed by removal of the solvents, the improvement comprises using aliphatic semicarbazide hydrazides of the formula wherein x is 1 or 2, as chain extenders.
  • Highly elastic polyurethane elastomer filaments having a breaking elongation of at least 300% and a heat distortion temperature above 145 C., consisting of linear segmented polyurethane elastomers with an inherent viscosity (as measured on a 1% solution in hexamethyl phosphoramide at 25 C.) of at least 0.5, containing intralinear segments with the structure in which D represents a long chain divalent aliphatic polymer radical having a molecular weight of from 600 to 5000 and a melting point below 60 C.; R represents a divalent organic radical of an aromatic, aliphatic, cycloaliphatic or araliphatic diisocyanate; G represents a divalent aliphatic, cycloaliphatic or araliphatic radical of a dihydric alcohol with a molecular weight of from 62 to 300, optionally containing 1 or more tertiary aliphatic amino groups; x is l or 2; r is an integer from
  • a spinning solution of polyurethane elastomers containing from 10 to 33% by Weight of substantially linear segmented polyurethanes with intralinear structures of a chain extending segment having the formula wherein x is 1 or 2, in a highly polar aliphatic solvent having amide, urea or sulphoxide groups and a boiling point of up to 225 C.
  • COLUMN I LINE ERROR 8 74 and N,N"-dimethylN,N'-bis" 75 should be N,N'bis 10 33 solution or dry: should be solution to dry l2 73 "Carbethoxyoxy” should be carbethyoxy 1? 10 "C N N O should be --C H N O 16 a Comp Ex d Line 4 'hydraxine” should be hydrazine 17
  • Example 4 “Example 4 should follow paragraph it now heads 18 Table 4 "Fitness ,Den” should be Fineness den 2 3 4 165%) should be 1.65%)
  • Example 21 under Residual Elongation "63" should be 36 Signed and sealed this 8th day of January 1974.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US830128A 1968-06-07 1969-06-03 Linear segmented polyurethane elastomers Expired - Lifetime US3640937A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19681770591 DE1770591A1 (de) 1968-06-07 1968-06-07 Lineare,segmentierte Polyurethanelastomere

Publications (1)

Publication Number Publication Date
US3640937A true US3640937A (en) 1972-02-08

Family

ID=5700565

Family Applications (1)

Application Number Title Priority Date Filing Date
US830128A Expired - Lifetime US3640937A (en) 1968-06-07 1969-06-03 Linear segmented polyurethane elastomers

Country Status (10)

Country Link
US (1) US3640937A (de)
AT (2) AT310928B (de)
BE (1) BE734194A (de)
CH (1) CH534191A (de)
DE (1) DE1770591A1 (de)
ES (1) ES368123A1 (de)
FR (1) FR2010399A1 (de)
GB (2) GB1247803A (de)
NL (1) NL6908673A (de)
SE (1) SE363838B (de)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3978156A (en) * 1975-05-14 1976-08-31 The B. F. Goodrich Company Color stabilized polyurethanes
US4070345A (en) * 1975-09-24 1978-01-24 Bayer Aktiengesellschaft Monomethylol ether diols and polyurethane solutions prepared therefrom
US4125693A (en) * 1973-11-03 1978-11-14 Chemie-Anlagenbau Bischofsheim Gmbh Process for the production of polyurethanes dissolved in a solvent and also their use for the production of fabricated shapes, especially of microporous structures
US4286014A (en) * 1978-01-31 1981-08-25 Toray Industries, Incorporated Composite sheet material
US4666966A (en) * 1985-03-26 1987-05-19 Asahi Kasei Kogyo Kabushiki Kaisha Polyurethane composition and a stabilizer thereof
US5055545A (en) * 1989-05-18 1991-10-08 Bridgestone/Firestone, Inc. Urethane-rubber adhesives based on azoester prepolymers and derivatives thereof
US5059647A (en) * 1989-09-29 1991-10-22 E. I. Du Pont De Nemours And Company Oligomeric semicarbazide additives for spandex
US5518764A (en) * 1994-03-22 1996-05-21 Bayer Aktiengesellschaft Process for coating textiles
US5656701A (en) * 1992-11-06 1997-08-12 Sakata Inx Corp. Polyurethane resins, process for producing the same, and uses thereof
US20040162387A1 (en) * 2003-02-14 2004-08-19 Thorsten Rische One-component coating systems
US20050085584A1 (en) * 2003-09-18 2005-04-21 Rudiger Musch Aqueous adhesive dispersions
US20050159541A1 (en) * 2004-01-16 2005-07-21 Bayer Materialscience Ag Size composition
US20050182188A1 (en) * 2004-01-16 2005-08-18 Bayer Materialscience Ag Coating material composition
US20050234190A1 (en) * 2004-04-08 2005-10-20 Rolf Gertzmann Process for the continuous production of an aqueous polyurethane dispersion
US7026429B2 (en) 2002-12-20 2006-04-11 Bayer Aktiengesellschaft Hydrophilic polyurethane-polyurea dispersions
US20140215948A1 (en) * 2011-08-09 2014-08-07 Karlsruher Institut für Technologie Method for reinforcing a building component
US8846174B2 (en) 2011-02-25 2014-09-30 Schott Corporation Transparent laminate structures
US9085713B2 (en) 2010-08-17 2015-07-21 Stahl International Bv Stable aqueous wax dispersions
US10590226B2 (en) 2015-04-21 2020-03-17 Covestro Deutschland Ag Solids based on polyisocyanurate polymers produced under adiabatic conditions
US10597484B2 (en) 2015-04-21 2020-03-24 Covestro Deutschland Ag Polyisocyanurate plastics having high thermal stability
US10717805B2 (en) 2015-04-21 2020-07-21 Covestro Deutschland Ag Process for producing polyisocyanurate plastics
US10745591B2 (en) 2015-04-07 2020-08-18 Covestro Deutschland Ag Method for adhesively bonding substrates using adhesives
US10752724B2 (en) 2015-04-21 2020-08-25 Covestro Deutschland Ag Process for producing polyisocvanurate plastics having functionalized surfaces
US10752723B2 (en) 2015-04-21 2020-08-25 Covestro Deutschland Ag Polyisocyanurate polymer and process for the production of polyisocyanurate polymers
US11384261B2 (en) 2016-04-04 2022-07-12 Tesa Se Radiation-activatable pressure-sensitive adhesive tape having a dark reaction and use thereof

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4433437A1 (de) 1994-09-20 1996-03-21 Bayer Ag Vernetzer für Textildruck-Bindemittel
DE19548030A1 (de) 1995-12-21 1997-06-26 Bayer Ag Verwendung wässriger Dispersionen nachvernetzbarer Beschichtungsmittel zur Textil- und Lederbeschichtung
WO2011144530A1 (en) 2010-05-17 2011-11-24 Bayer Materialscience Ag Process for joining together components, in particular in the production of shoes
EP2387900A1 (de) 2010-05-17 2011-11-23 Bayer MaterialScience AG Verfahren zum Zusammenfügen von Bauteilen, insbesondere in der Herstellung von Schuhen
EP2441791A1 (de) 2010-10-14 2012-04-18 Clariant International Ltd. Stabile wässrige Wachsdispersionen
WO2012117416A1 (en) 2011-03-01 2012-09-07 Roidec India Chemicals (P) Ltd. A non-plastic and biodegradable aqueous natural oil based lacquer for food grade flexible packaging
WO2012117414A1 (en) 2011-03-01 2012-09-07 Roidec India Chemicals (P) Ltd. Process for the preparation of a natural oil based poly-urethane dispersion
MX2013010022A (es) 2011-03-01 2013-09-26 Roidec India Chemicals P Ltd Dispersion de poliuretano con base de aceite natural.
DE102022105185A1 (de) 2022-03-04 2023-09-07 Tesa Se Lösbares Laminat und Verfahren zum Lösen dauerhafter struktureller Verklebungen

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4125693A (en) * 1973-11-03 1978-11-14 Chemie-Anlagenbau Bischofsheim Gmbh Process for the production of polyurethanes dissolved in a solvent and also their use for the production of fabricated shapes, especially of microporous structures
US3978156A (en) * 1975-05-14 1976-08-31 The B. F. Goodrich Company Color stabilized polyurethanes
US4070345A (en) * 1975-09-24 1978-01-24 Bayer Aktiengesellschaft Monomethylol ether diols and polyurethane solutions prepared therefrom
US4286014A (en) * 1978-01-31 1981-08-25 Toray Industries, Incorporated Composite sheet material
US4666966A (en) * 1985-03-26 1987-05-19 Asahi Kasei Kogyo Kabushiki Kaisha Polyurethane composition and a stabilizer thereof
US5055545A (en) * 1989-05-18 1991-10-08 Bridgestone/Firestone, Inc. Urethane-rubber adhesives based on azoester prepolymers and derivatives thereof
US5059647A (en) * 1989-09-29 1991-10-22 E. I. Du Pont De Nemours And Company Oligomeric semicarbazide additives for spandex
US5656701A (en) * 1992-11-06 1997-08-12 Sakata Inx Corp. Polyurethane resins, process for producing the same, and uses thereof
US5518764A (en) * 1994-03-22 1996-05-21 Bayer Aktiengesellschaft Process for coating textiles
US7026429B2 (en) 2002-12-20 2006-04-11 Bayer Aktiengesellschaft Hydrophilic polyurethane-polyurea dispersions
US20040162387A1 (en) * 2003-02-14 2004-08-19 Thorsten Rische One-component coating systems
US20050085584A1 (en) * 2003-09-18 2005-04-21 Rudiger Musch Aqueous adhesive dispersions
US20050159541A1 (en) * 2004-01-16 2005-07-21 Bayer Materialscience Ag Size composition
US20050182188A1 (en) * 2004-01-16 2005-08-18 Bayer Materialscience Ag Coating material composition
US7276554B2 (en) 2004-01-16 2007-10-02 Bayer Materialscience Ag Coating material composition
US20050234190A1 (en) * 2004-04-08 2005-10-20 Rolf Gertzmann Process for the continuous production of an aqueous polyurethane dispersion
US7345110B2 (en) 2004-04-08 2008-03-18 Bayer Materialscience Ag Process for the continuous production of an aqueous polyurethane dispersion
US9085713B2 (en) 2010-08-17 2015-07-21 Stahl International Bv Stable aqueous wax dispersions
US8846174B2 (en) 2011-02-25 2014-09-30 Schott Corporation Transparent laminate structures
US9546490B2 (en) * 2011-08-09 2017-01-17 Covestro Deutschland Ag Method for reinforcing a building component
US20140215948A1 (en) * 2011-08-09 2014-08-07 Karlsruher Institut für Technologie Method for reinforcing a building component
USRE48584E1 (en) * 2011-08-09 2021-06-08 Covestro Deutschland Ag Method for reinforcing a building component
US10745591B2 (en) 2015-04-07 2020-08-18 Covestro Deutschland Ag Method for adhesively bonding substrates using adhesives
US10590226B2 (en) 2015-04-21 2020-03-17 Covestro Deutschland Ag Solids based on polyisocyanurate polymers produced under adiabatic conditions
US10597484B2 (en) 2015-04-21 2020-03-24 Covestro Deutschland Ag Polyisocyanurate plastics having high thermal stability
US10717805B2 (en) 2015-04-21 2020-07-21 Covestro Deutschland Ag Process for producing polyisocyanurate plastics
US10752724B2 (en) 2015-04-21 2020-08-25 Covestro Deutschland Ag Process for producing polyisocvanurate plastics having functionalized surfaces
US10752723B2 (en) 2015-04-21 2020-08-25 Covestro Deutschland Ag Polyisocyanurate polymer and process for the production of polyisocyanurate polymers
US11390707B2 (en) 2015-04-21 2022-07-19 Covestro Deutschland Ag Polyisocyanurate polymers and process for the production of polyisocyanurate polymers
US11384261B2 (en) 2016-04-04 2022-07-12 Tesa Se Radiation-activatable pressure-sensitive adhesive tape having a dark reaction and use thereof

Also Published As

Publication number Publication date
CH534191A (de) 1973-02-28
GB1247803A (en) 1971-09-29
ES368123A1 (es) 1971-05-01
BE734194A (de) 1969-11-17
SE363838B (de) 1974-02-04
DE1770591A1 (de) 1971-11-04
AT292310B (de) 1971-08-25
FR2010399A1 (de) 1970-02-13
NL6908673A (de) 1969-12-09
GB1247802A (en) 1971-09-29
AT310928B (de) 1973-10-25

Similar Documents

Publication Publication Date Title
US3640937A (en) Linear segmented polyurethane elastomers
US3658746A (en) Segmented polyurethane elastomers
US2941966A (en) Carbodiimide polymers
US3635870A (en) Segmented polyurethane elastomers
US3597398A (en) Spandex polymers of polymeric diols,functionally aliphatic diisocyanates and non-hindered functionally aliphatic diamines
US4791187A (en) Linear polyurethane elastomers, and a process for the preparation thereof
US3377308A (en) Two-step process for the production of solutions of segmented polyurethane polymers
US3432456A (en) Polyurethanes prepared from dihydrazides
US3857809A (en) Polyurethane-ureas based on cis-trans-1,4-diaminocyclohexane
US4153775A (en) Self-crosslinkable polyurethanes
DE2034538C3 (de) Verfahren zur Herstellung von mikroporösen Flächengebilden
US4446293A (en) Low-solvent, thermosetting reactive polyurethane coating composition, a process for its production and its use in direct and reverse coating processes
EP0208226A2 (de) Urethanüberzug-Zusammensetzungen auf Wasserbasis
US3630987A (en) Linear segmented polyurethane elastomers
US3415790A (en) Removing unreacted diisocyanates from macrodiisocyanates and polymerizing to form segmented polyurethane copolymers
US3040003A (en) Synthetic polymers
US3401151A (en) Polyurethanes having improved dyeability
US3711443A (en) Linear segmented polyurethane elastomers
US2888440A (en) Polyurethane diamines
US3719708A (en) Beta-semicarbazide propionic acid hydrazide
US4192928A (en) Thermoplastic polyurethane and process for the preparation thereof
US3404131A (en) Elastic fibers and films
US3365412A (en) Polyurethane fibers and foils
US3708453A (en) Linear segmented polyurethanes
US3763058A (en) Polyurethane elastomers with high affinity for dyes